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S. V. Panyukov
P. N Lebedev Physics Institute, Moscow
1. INTRODUCTION
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and 12. The results that we obtain do not agree with the
results of these papers. Therefore, first and foremost, the
question of the applicability of the corresponding approaches arises.
In contrast to the variational estimates of Refs. 10-12,
the method that we use is a regular expansion in a small
parameter, which we find in Sec. 3. The reason for the differences under discussion is buried in the specific physical features of the problem under consideration. A large number of
potential wells with a broad distribution of sizes cannot be
simulated by a single-well potential in the framework of a
variational approach.
From the experimental point of view, the most interesting realization of the systems under consideration here is
provided by chains immersed in a polymer network. The
theory of small-angle neutron scattering by these chains in
such a polymer system was constructed in Refs. 5 and 6, and
below we shall give a brief review of the corresponding experimental data.
In Refs. 14 and 15 a study was made of the influence of
the degree of crosslinking X of the network (as judged from
the degree of equilibrium swelling of the network) on the
intensity of small-angle neutron scattering by free deuterated chains situated in the network. For small values of X the
intensity turns out to be the same as in the case of a mixture
of deuterated chains with uncrosslinked network chains of
the same density. Under uniaxial deformation of the
network the signal increases strongly in the direction parallel to the stretching, but remains unchanged in the perpendicular direction (see Fig. l a ) .
In the case of intermediate values of X the scattering in
the swollen state of the network is greater than that by a
mixture of uncrosslinked chains. Upon stretching, the signal
increases in the direction parallel to the stretching and decreases in the perpendicular direction, returning, with increase of the stretching, to its value for the mixture (Fig.
lb).
In the case of large values of X the scattering in the
swollen state is considerably greater than the scattering by a
mixture of uncrosslinked chains. In the direction parallel to
the stretching the signal does not change with increase of the
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take the normalization condition (4) into account by introducing a Lagrange multiplier p. The minimization of the
functional (4) leads to an equation of the Schrodinger type
for the function $(x) = c'" (x), with eigenvalues ~ { u )= p:
and the free energy (4) of the chain takes the form
a) General theory
where the bar denotes averaging over the random realizations of the field u (x). The probability measure of the distribution of such a field has the form
W(u(x)) = const exp [-S{u(x))] ,
s{u(x)) = 112JdxJdx~~(x- x~)u(x)u(x~),
(2)
- XI).
The minimum of Fo(6) is reached when E = E, is the smallest eigenvalue of ~ q ( 3. ), corresponding to the eigenfunction 9 = $w
The key to the solution of the problem under consideration is provided by going over from the random field ( x ) to
an abbreviated description of the disorder in terms of the
variable E~{u),which is given implicitly by Eq. (5). Typical
realizations of the potential u(x) have the form of rather
deep potential wells, randomly distributed in the sample.
The probability of finding a well with a given value
E = E ~ { u ) is given by the expression
(3)
Taking this condition into account with the aid of a Lagrange multiplier A, from the condition for the minimum of
the functional S{u) with respect to u(x) we find an expression for the optimal fluctuation of the field u(x) in terms of
the function 1Cl,(x):
S. V. Panyukov
632
Therefore, the condition IF,I ) T for the existence of the solution under consideration can be represented in the form
I,Imi, = ( R / a ) 2 .Sufficientlyshort chains with 1 <Imi, have
Gaussian size R = a1 ' I 2 .
c) Localizationof branched polymers
= v~(x),
v = Jdxv(x),
(14)
The logarithmic term in ( 2 0 ) describes the change of entropy of an elementary chain when it is localized from the
free state, in which is occupied volume ( a N ' I 2 )3, down to the
volume R 3.
The relation ( 2 0 ) was first obtained by us in the framework of the replica f~rmalism,~'
but, because of the transparency of its physical meaning, there is no need to give a rigorous derivation of it here.
3. FREE ENERGY OF A POLYMER CHAIN
where w, is the second virial coefficient. Following the method of Ref. 22, we expand the desired solution that minimizes
the free-energy functional ( 2 1 ) in the eigenfunctions of Eq.
(3):
The coefficients c, are found by substituting the expansion ( 2 2 ) into the functional (21 ) and minimizing the resulting expression with respect to the c,. Below, we show
that in the localized region it is sufficient to confine ourselves
to taking into account the single term with k = 0 . In this
approximation we find for the coefficient c, the expression
The Lagrange multiplierp is found by substituting the solution obtained for p ( x ) into the second equality (4):
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S.V. Panyukov
633
p = lei - ~ ~ w , l a - ~ l e l ~B;'l ~ =
, 2Ad(l - d/412. ( 2 4 )
Fin,(R) = T B ~ W ~ ~ ~( 2I 5~) R ~ ,
la)'.
(26)
- pllel
= 111-,
(27)
where we have made use of the expression ( 2 4 ) for the par a m e t e r ~Thus,
.
the expressions ( 2 5 ) and ( 1 9 ) fully determine the free energy of a chain for which the number I of
links lies in the interval ( 2 6 ) . Chains with I< I,,, have
Gaussian statistics (the free energy IF I T , and the size
R = a1 ' I 2 ) .
--
tity g , < I,,, for v > xw,, as a consequence of the above-indicated effect of partial expulsion of the chain from the potentials wells. Thus, the perturbation-theory parameter g,/l,,,
( 2 7 ) is indeed small. The results ( 2 9 ) also make it possible
to convince oneself that the interaction of the monomer links
inside a tube is small. In fact, the corresponding perturbation-theory parameter16
(29)
is small for v > xw,. This condition also guarantees fulfilment of the inequality F, < 0 .
4. AVERAGE SIZE OF A POLYMER CHAIN
a) Three-particleinteraction(the 0-conditions)
S. V. Panyukov
634
Equation (36) demonstrates the difference between statistical (quenched) averaging and the ordinary Gibbs (annealed) average. In the latter case the dependence R I implies that the chain is stretched out into a string. In reality, it
finds sparsely located potential wells with size (36), which
have, on the average, the shape of a sphere.
In the case of weak disorder ( u < w,) there is no extrema1 point and the size of the chain is determined by the contribution of the delocalized states [which were not included
in the definition ( 3 1) 1 :
c) Long-range interaction
(42)
R~ = a4/391312,
i>(a~w)~~~.
(44)
I /g, potential wells threaded onto such a string, for the paS.V. Panyukov
635
In statistical physics we consider two types of disordered systems-those with mobile (annealed) disorder and
those with frozen (quenched) disorder. In correspondence
with this classification we consider two types of polymer
networks-physical and chemical. The topological (chemical) structure of physical networks is annealed, and the formation and breaking of the chemical crosslinks between the
chains of such a network is described by the condition of
chemical equilibrium. The topological structure r of chemical networks is fixed by the conditions of the synthesis. The
physical properties of the two types of networks are substantially different: Physical networks are liquid, whereas chemical networks are solid. At the same time, as will be shown
below, the characteristics of these networks turn out to be
closely related to each other.
We shall denote by SPhb) and Sh@,A) the entropies
of a physical and a chemical network, respectively, with a
given density p ( x ) of links:
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r to integration over the distribution n (x), we find a relationship between the parameters of physical and chemical
networks:
The function x has been calculated in Refs. 26 and 27 by
the replica method for networks obtained by equilibrium
crosslinking of long chains. In the long-wavelength limit
q -0 they have the form
p, =
Here and below, the superscript (0) indicates that the coresponding quantity pertains to the conditions of synthesis.
The quantities u, and B, appearing in (52) have the
form
The function G
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We substitute into (61) the expression (56) for the probability and the expression (52) for the free energy. The Gaussian
integrals in (6 1) are calculated by going over to the Fourier
representation:
Here, G, has the meaning of the correlation function of thermodynamic (temporal) fluctuations of the density of monomer links, and C, is the correlation function of statistical
(spatial) fluctuations of the density. The magnitude of the
latter fluctuations can also be found from the condition for
S. V. Panyukov
637
The quantity I, (62) that we have calculated is proportional to the intensity of the small-angle scattering of neutrons by deuterated chains. Substituting into (62) the
expression (56) for v, and making use of the expression
(51) for the functions x , we find that, depending on the
relative magnitudes of A (the degree of swelling of the lattice) and the parameter X = cl / p N < 1, three basic regions
must be distinguished:
a ) The case A < X - ' I 4 can be realized for small X. Under uniaxial stretching of such networks the intensity I,
(62) of scattering by free chains behaves in accordance with
Fig. la.
b ) The case X - ' I 4 <A < X - ' I 2 occurs for intermediate
values ofX. The dependence of the intensity I, on the degree
of uniaxial extension of the network is found in accordance
with Fig. lb.
c ) The Case A > X - ' I 2 is realized for sufficiently large
X. The intensity I, depends on the degree of extension of the
network in accordance with Fig. lc.
c) Partially deuterated chains
one end are localized in the nearest region with the size R,,, .
Free chains are localized in sparsely located but deeper energy wells. Because of the presence of the repulsive interaction,
it is energetically more favorable to distribute chains with
I > I,,, over several wells.
An important application of the theory developed here
is to a system of linear chains placed in a polymer network.
We have shown that the correlation function u characterizing the disorder in such a random medium can be expressed
directly in terms of correlation functions of the polymer networks. The latter have been found previously in Refs. 26 and
27. In the case of isotropic stretching of the network by a
factor ofA we obtained u = 5A ' w 2 / 3 .Thus, the relation between the effective interaction parameter w 2and the disorder u can be changed by stretching the network, thereby
scanning in a single sample all the localization regimes predicted above. In this sense polymer networks are an ideal
object for the study of localization of polymers.
The physical picture of the localization of isolated
chains differs substantially from the picture of the ordering
of the overlapping chains of a polymer solvent. In the former
case improbable fluctuations of the random field correspond
to localized states, while in the latter case only typical values
of this field are important.
We have shown that isolated chains that are localized in
one potential well are ordered in a direction perpendicular to
the direction of stretching of the elementary chains of the
network during uniaxial stretching of the network, this effect being anomalously strong: AR / R =. - M /A. At the
same time, according to the expression (65) for @ +O, the
individual chains of a polymer solvent experience practically
no orientational ordering. The experimentally observed anisotropy of the scattering is due to the collective effect of the
interaction of the totality of these chains with nonuniformities of the polymer network. We have shown that the theory
proposed by us for the anisotropic scattering is in good
agreement with the experimental data discussed in the Introduction.
The author expresses his gratitude to J. Bastide and F.
Boue for the opportunity to become acquainted with the experimental data of Ref. 15 and for discussion of some the
results of the present paper.
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